Phenol esters of silicon oxychlo



Reissuecl Sept. 26, 1950 RIDES AND METHOD THEM F PRODUCING VaughanMorrill, In, St. Louis, Mo., assignor to American Stove Company, St.Louis, Mo., a corporation of New Jersey No Drawing. Original No.2,416,531, dated February '25, 194.7, Serial No. 507,763, October 26,.1943. Application for reissue November .4, 1947.

Serial No. 784,068

4 Claims. '(Cl. 260448.8)

Matter enclosed in heavy' brackefslI 1 appears in the original, patentbut forms no p 01' t reissue specification; matter printed in italicsindicates the additions made'by reissue This invention pertains to anewcomposition of matter, often commonly referred to as-a new product, andthemethod of making the same.

More articularly and specifically the new product results from achemical reaction between phenol (CsI-IsOH) and the silicon oxychloridegroup and is a phenol silicate.

The new compound isproduced by the following described methodwhich-although it produces a product which is satisfactory in allrespects may not, on further research, prove to be either the mostsatisfactory, economical or desirable method possible to evolve tor theproduction of the product.

The first step is the production of silicon oxychlorides which is donein the following manner. Lump silicon (98% .pure) orof-purity from 50%up of silicon in ferro-silicon, is heated to approximately 1200'F. in-suitable furnace or retort. The temperature reached is not critical andcan safely vary between 1000 F; and'1500" F. Oxygen and chlorine arepassed over the hot silicon and produce a mixture composed of the groupof silicon oxychlorides and silicon tetrachloride. This mixture emergesfrom the retort or furnace as a vapor which is condensed and at roomtemperature is in the ,form of a liquid having an amber color. The groupof silicon oxychlorides are separated .fromthesilicon tetrachloride byfractional distillation. Silicon tetrachloride and the siliconoxychlorides present before separation by distillation are in proportionto one another which may be varied by regulating the rates of flowofchlorine and oxygen passed over the hot-silicon. By increasing thepercentage of chlorine passed over the hot silicon the resulting productwill be high in the percentage of silicon tetrachloride while areduction in the percentage of chlorine and an increase in thepercentageof oxygen passed over the hot silicon willcausetheresultingzprodnot to contain a higher percentage of siliconoxychlorides.

The production of silicon :oxychlorides is not new and their productionthoroughly described in an article byW. C. Schumb and D. F. Hollowaywhich appears in the Journal of the American Chemical Society, volume63, of October 1941, pp. 2753-55. This article is believed to give themost authoritative-data on oxychlorides-of silicon and gives, for thefirst time, the analysis of some of the oxychlorides in the group.

Reference should be had to said publication for a detailed study of thesilicon oxychloride group. 7 Among other things said article makes itclear that the group of silicon oxychlorides resulting from the chemicalreaction of chlorine and oxygen on lump silicon at a dull red heat canbe separated by fractional distillation and were found to be of thefollowing formulas:

I: (SiOClzl-i] S1403 C110. SizOCls SRO-10112 SiaGzCla -SisOsClm Si4O4Cla.SizOsChs This article states that isolation of still higher members ofthe homologous series becomes almost impossible for the reason that theboiling point difference between each compound becomes less and less andthe percentage differences in composition become too small for positiveidenti fication.

The article further recites that the substances separated out byfractional distillation, except the tetramer which is a colorlesscrystalline solid, are colorless, oily liquids increasing in viscositywith increasing molecular weight being hydrolyzed in the presence ofmoisture and being miscible with carbon tetrachloride, chloroform,carbon disulfide and silicon tetrachloride.

So far as the present invention is concerned the group of siliconoxychlorides are considered and treated as a, single substance inasmuchas the group is difficult'to separate into the separate products makingup the group and are so similar as to make the products individuallyunimportant so far as the final product of :this invention is concerned.

The next step in the method for producing my new product consists inchemically reacting. phenol (CsHsOH) with the group of siliconoxychlorides. The reaction is carried on or performed in a suitablemixing vessel. The phenol is mixed at-room temperature and'atrnosphericpressure with the silicon oxychlorides and they are gradually heated toapproximately 850 F. When the phenol and oxychlorides are mixed hydrogenchloride is evolved. As the mixture is gradually heatedhydrogen'chloride continues to evolveu-ntil the mixture hasreached atemperature of approximately 400 ;F. When the mixture has reached thistemperature substantially all of the hydrogen chloridehas been. removedfromiche compound and upon carryingthe mixzturexgradually up toatemperatureofBSOF. the phenol silicates are boiled. oil. The rate ofheating is gradual to prevent too rapid a reaction which if it occurred,would cause some of the oxychlorides to boil off before the reactionwith the phenol had taken place. The phenol silicates boiled off of themixture are collected in a condenser as a single mixture which as aproduct is a clear to amber-colored liquid. amount of heavy tar-likesubstance will be pres,- ent in the mixing vessel or retort and the 850F1. temperature is maintained until this residue is practically a solid.The residue is in all probability free silicon from the distillation ofsilicon hydrochlorides under heat' This residue is discarded.

To insure a complete reaction, of the silicon oxychlorides with thephenol an excess of phenol is added to be present in the mixture. Inactual practice it has been found desirable to add, by weight, phenol inapproximately twice the amount of the silicon oxychlorides. It would bedifiicult to determine accurately the theoretical,

amount of phenol. required as the exact percent ages of the variousoxychlorides in the new product is not known nor is it known howcompletely each of the oxychlorides reacts with the phenol.

The phenol silicates obtained by the described chemical reaction betweenphenol and the group of silicon oxychlorides are as follows:

All of the phenol silicates fall within the general formula:

sinon uosnfioma j where n is greater than 1 with the exception of [thefirst in the list which is the result of the tetramer and the fifth inthe list which is} the cyclical SL104 (CaHsOhz. Thus, although [thefirst and. fifth phenol silicates do not follow in] the cyclical doesnot have the general formula [they fall within it], it is consideredpart of this group because it is well known in the chemical art that[these] this phenol silicate is of the same group [withl as the otherphenol silicates. That it would be so recognized is evidenced by theSchumb and Holloway referred to report.

The new product is useful and valuable for the purposes hereinafterenumerated and it is believed that further research will reveal a muchwider and varied field of use than it is possible at the present stagewhich has been reached in the research to enumerate or foretell.

It has been found that the product has great stability over a wide rangefrom low to high temperatures and also a high dielectric strength. Theseattributes will, it is believed, give broad and general usages ofthe'product as a transformer oil; as an electrical insulating medium,and as a paint plasticizer.

I claim:

1. The process for producing a mixture of phenol silicates comprising,mixing for chemical reaction phenol with a mixture of siliconoxychlorides comprising SizOCls; SisOzCls; Si404C1s; Si4O3C11u;Si5O4C112; SieOsClm; and Shoe-C116, heating said mixture and driving offtherefrom substantially all of the hydrogenchloride therein, continuingsaid heating and condensing the vapor driven 011 by said continuedheating'to A small and Si'7Os(CsH5O)1s.

2. The process forproducing [phenol silicates comprising, mixing phenoland a mixture of silicon oxychlorides comprising SizOCIs;

- v SisOzCla Si404CIa; Si403C; Si504C112; SisOsClm; and Si'iOsChs forchemical reaction and heating said mixture to approximately850 F., andcollecting and condensing the vapors. of said mixture after the mixturehas reached a temperature of approximatel 400 F.

3. Anew product resulting from the chemical reaction of phenol and amixture of oxychlorides of silicon comprising SizOCle; SiaOzCla;Si404C18; Si4O3C11o; 815040112; SieOsClm; and SiwOeClis, said compoundbeing characterized by being stable at all temperatures between 0 F. and800 4. A high boiling point product comprising phenol silicates obtainedby reacting phenol with a mixture of silicon oxychlorides comprisingSizOCls; SiaOzClsj S14O4C1a; Si4O3C11o;

SisO5(CsH5O)14,' and Si'zOs(CsH50)16; said product being stable at alltemperatures between 0 and 800 F., and being non-corrosive to stainlesssteel, iron, copper or brass. V

- VAUGHAN 'MORRILL, JR.

REFERENCES CITED 7 The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,317,891 Dennison Apr. 27; 19432,335,012 Johnston Nov. 23,1943

FOREIGN PATENTS Number Country Date 86,131 Austria Nov. 10, 1921 168,659Great Britain Feb. 5, 1921 OTHER REFERENCES Hertkorn: Berichte der Deut.Chem. Gess,"

vol. 18 (1885), pages 1679-1699.

Schumb: Jour. Amer. Chem. Soc, vol. 63 (1941), pages 2853-4.

Schumb: Jour. Amer. (1941), pages 2753-5.

Beilstein: Handbuch der Org. Chem, vol. VI, 4th ed., page 182.

Signer: Annalen der Chemie," 54-73, 1931.

Konrod: Annalen der Chemie, vol. 474, pages 27fi-295, 1929.

Pellini: Gazz. Ohim. Ital, vol. 45I, pages 38-5, 1915.

Chem. Soc., vol. 63

vol. 488, pages

